Treatment of petroleum products



' provide a process for boiling alkyl benzenes.

Patented Oct. 7, 19 41 UNITED STATES PATENT OFFICE- zaamzo. I I I TREATMENT OF PETROLEUM PRODUCTS Alexander N. Sachanen and Rowland 0. Hans- !ord, Woodbury, Vacuum Oil N. 1 Company, Incorporated, New

assignors to Socony- Yorlr, N. Y.', a corporation of New York No Drawing.

Application January 20, 1939, Serial No. 251,914

3.Claims. (o1. Mil- 672) 1 invention relates to the production of arolenes by this process of transfer of side chains to benzene. No alkyl aromatics are obtainable irorn the purely naphthenic products in the transferred from the alkyl naphthenes.

agents because of their high anti-knock characteristics. As a result of this increased impor-. tance of the alkyl-substituted aromatic compounds various processes have been suggested for their preparation. However, so far as is known, no one has touched upon-our novel process of using certain petroleum products in the preparation of these compounds.

It is an object of this invention to provide a 7 process for the preparation of valuable aromatic compounds with the use of petroleum prodt A more specific object of the invention is to treating certain petroleum products, including waste hydrocarbon by prodnets of petroleum refining, whereby substantial yields are obtained of benzene and naphthalene derivatives.

Still another specific objectoi the invention is to provide a process for treating certain petroleum products, including hydrocarbon by-prodpetroleum stock except those alkyl benzenes produced by the'alkylation of benzene by side chains the conditions of the present process no appreciable dehydrogenation of naphthenes to aromatics is possible. This is in contrast to our high temperature dealkylation process for these same petroleum stocks disclosed and claimed in the co-pending application S. N. v227,9'7'7, filed September 1, 1938, now U. S. Patent 2,223,133, issued November 26, 1940.

It has been known to dealkylate synthetic alkyl' benzenes heretofore, however such prior processes are to be clearly distinguished from the present important discovery. The known dealkylation of alkyl benzenes has been carried out on relatively simple synthetic alkyl benzenes formed by alkylating benzene with olefines, On

the other hand we have discovered certain industrial petroleum products as, for instance, complex industrial by-products such as solvent tars from the solvent refining of petroleum oils or 1 the cracked residuum from petroleum cracking nets of petroleum refining, whereby substantial yields are obtained of aromatic compounds boiling within the gasoline boiling range, as well as substantial yields of allryl benzenes and alkyl naphthalenes boiling up to about 300 G.

Our invention is based upon the discovery that certain petroleum prpducts may be treated with benzene at relatively low temperatures of the nature herein disclosed in the presence of suitable catalysts to produce substantial yields of valuable benzene and naphthalene derivatives.

The reactions which appear to be involved in our process comprise the transfer e! side chains from various complex molecules of the petroleum product tothe molecules of the admixed ben- 'zene. This results in a consumption of benzene.

The consumption of benzene 'may or may not becnearly equivalent to the amount of the newio'rmed alk'yl benzenes, depending .on the quantity of more or less highly alkylated benzenes in the petroleum stock which may be sufllclenfly dealkylated to give an additional amount of lower H h boiling alkyl nsvh in the petroleum stock thsle'nesinitially present boiling alkyl naphthaare converted to lower processes which may be treatedto eflect a dealkylation of the various more or less complexmolecules therein, In the present process not only simple alkyl benzenes but also alwl derivatives of rather complex polycyclic aromatic hydrocarbons as well as those of 'naphthenic hydrocarbons are subjected to dealkylation. Moreover, by our process not only is a substantial yield of alkyl benzenes'in the gasoline boiling range obtained, but also a substantial yield of alkyl benzenes and alkyl naphthalenes boiling below about 800 F. is obtained. Quite obviously no alkylnaphthalenes are produced by the known dealkylation process above mentioned.

. That a sharp distinction exists between the present process and the above-mentioned prior art processes is established perhaps most clearly' bythe factthatsulfuric acidjwhichisdisclosed asaneflectiveeahlysti'orthesepriorartproc-.

esrleacannotbemedasacatalystinourproeess. Assoureesotpetroleummaterialtobetreated atten ,tiontosclvmtturswhich, asiiswellknowmare theby-productiromthe present-day solvent refining proeeses of Accordingly, by ourproeeswenotonlyaflord meansotobtain. ing valuable aromatic products but alsoaiford,ause for amaterial whichisnow usually-considered Under.

awasteby-product oi .F. In thepreferred form of ing aluminum chloride as a sider a'temperature around 180 F. to be the petroleum industry. In addition to the solvent tars, it is. to be clearly understood that the present process is applicable to the treatment of many other petroleum products and in fact is applicable to the treatment of any petroleum product containing substantial amounts of aromatic or naphthenic hydrocarbons. For instance, the petroleum products containing a considerable amount of aromatic or naphthenic hydrocarbons which are to be treated may include petroleum residues such as solvent and cracking tars and straight run residua. Moreover high boiling distillates (including distillates from tars) may be to these ratios but rather contemplates the broad use-of benzene in any amount sufficient to give our novel results.

The invention may be further illustrated by the following data obtained from the treatment of a Mirando furfural solvent tar with benzene.

It is to be understood that these specific treatments are not to be considered limiting as there may be variations therefrom without departing from the scope of the invention. The reaction f. mixture in both treatments comprised 1 part treated] The distillates may be any distillates.

boiling in the'range of kerosene or higher and containing substantial amounts of aromatic or naphthenic hydrocarbons. Some specific exam-- ples of petroleum material suitable. for treating, which are mentioned here merely for illustrative purposes, include Mirando, Rodessa, and East Texas furfural solvent tars from neutrals (distillates of lubricating oil fractions), Pennsylvania chlorex solvent tar from neutrals, dewaxed distillates, burning and power kerosene vdistillates, naphthenicdistillate for cracking, distillate from an Ellis (coil and drum) cracked residuum and an Ellis cracked residuum. For the best yields it is desirable to use petroleum products containing a predominant portion of arcmatic or naphthenic hydrocarbons. Petroleum products containing less amounts may be used but the yields are correspondingly less.

The catalytic material to be used in our process must be capable of promoting dealkylation reactions of our petroleum products under the con- "aluminum chloride.

Mirando furfural tar, 2 parts benzene and 10% It is to be noted that this Miranda tar did not contain initially any dis-'- tillates boiling below 315 C.

1. Theprpcess'of producing alkyl aromatic hy. drocarbons boiling below about. 300 C. from a petroleum tar comprising a substantial amount ditions of the process. Catalysts of the nature of heavy metal halides as, for example aluminum chloride, aluminum bromide, zirconium chloride and zinc chloride are suitable. In our preferred operation we employ aluminum chloride asthe catalyst. However, it is to be noted particularly, as mentioned hereinabove, that an-acid catalyst such as sulfuric acid is not operative in the present process, it having been found that sulfuric acid, has a negative eifect in the de- 1 alkylation of petroleum products according to our process. For best results the temperatures employed in our process should be effective operating temperat'ures :which are below about 400, F. and

preferably between about 175 F. and about 250 the invention, us-

most desirable.

From a practical standpoint we have found a ratio of benzene to stock treated of about V.

' volume to 2 volumes of benzene to 1 volume of proper proportion'ing for ob- I taining our'desiredresults. It is to be understood, however, that the invention is not limited stock usually. gives catalyst; we con-- of alkyl aromatic hydrocarbons entirely of petroleum origin which are normally found in such tar and are of higher boiling point than said alkyl ammatic hydrocarbons to be produced,

which comprises treating such alkyl aromatic hydrocarbons of said tar with benzene in the h presence of a metal halide catalyst at a temperature between about C. and about 200C.

2. The process of producing alkyl aromatic hydrocarbons boiling below about 300 C. from a petroleum tar comprising a substantial amount of alkyl aromatics entirely of petroleum origin which are normally foundin such tar and are of higher boiling point than said alkyl aromatics to be produced, which comprises treating said petroleum tar with benzene in the presence of an aluminum chloride catalyst at a temperature between about 80 C. and about 200 C.

3. The process of producing alkyl benzenes and alkyl naphthalenes boiling below about 300' CL- from a petroleum solvent tar comprising a substantial amount ofalkyl aromatics entirely of petroleum origin which are normally found in such tar and are of higher boiling point than said alkyl aromatics to be produced, whichcomprises treating said petroleum solvent tar with benzene in the presence of -an aluminum chloride catalyst at a temperature between about 80 C. and about- C..

' ALEXANDER N. sAcHANEN. ROWLAND c. HANsFfoRD. 

